α-methyl-(6-phenoxy)-2-picolyl cyclopropanecarboxylates having pesticidal properties

ABSTRACT

The invention relates to α-methyl-(6-phenoxy)-2-picolyl cyclopropanecarboxylates of the formula ##STR1## wherein X 1  is methyl or halogen, 
     R 1  is hydrogen or halogen, and 
     R 2  is hydrogen, halogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 1  -C 4  alkylthio, C 1  -C 4  haloalkyl, C 1  -C 4  haloalkoxy, C 1  -C 4  haloalkylthio, C 2  -C 4  alkenyl, C 2  -C 4  alkynyl, nitro or cyano. 
     The invention also relates to the preparation of these esters and to the use thereof in pest control.

The present invention relates to α-methyl-(6-phenoxy)-2-picolylcyclopropanecarboxylates, to the preparation of these esters and to theuse thereof in pest control.

The α-methyl-(6-phenoxy)-2-picolyl cyclopropanecarboxylates have theformula ##STR2## wherein X₁ is methyl or halogen,

R₁ is hydrogen or halogen, and

R₂ is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio,C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, C₁ -C₄ haloalkylthio, C₂ -C₄alkenyl, C₂ -C₄ alkynyl, nitro or cyano.

Halogen in the above definition is fluorine, chlorine, bromine oriodine.

The alkyl, alkoxy, alkythio, haloalkyl, haloalkoxy, haloalkylthio,alkenyl and alkynyl groups may be straight chain or branched. Examplesof such groups comprise methyl, methoxy, methylthio, trifluoromethyl,trifluoromethoxy, ethyl, ethoxy, propyl, isopropyl, n-butyl, vinyl,1-propenyl, ethynyl, 1-propynyl.

Particularly preferred compounds of formula I are those wherein

X₁ is methyl or chlorine,

R₁ is hydrogen or halogen, and

R₂ is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio,vinyl or ethynyl.

The most preferred compounds of formula I are those wherein

X₁ is methyl or chlorine,

R₁ is hydrogen, and

R₂ is hydrogen or halogen.

The compounds of formula I are prepared by methods which are known perse, e.g. as follows: ##STR3##

In formulae II to V, R₁, R₂ and X₁ are as defined for formula I.

In formulae II and III, one of X and X' is a hydroxyl group and theother is a halogen atom, preferably chlorine or bromine, or both X andX' are a hydroxyl group, and in formula IV, R is C₁ -C₄ alkyl,preferably methyl or ethyl. Suitable acid acceptors are in particulartertiary amines, such as trialkylamine and pyridine, and alsohydroxides, oxides, carbonates and bicarbonates of alkali metals andalkaline earth metals, and in addition alkali metal alcoholates, forexample potassium tert-butylate and sodium methylate. As hydrophilicagent, it is possible to use e.g. dicyclohexylcarbodiimide. Processes 1and 2 are carried out at a reaction temperature in the range from -10°to 120° C., usually from 20° to 80° C., under normal or elevatedpressure and preferably in an inert solvent or diluent. Examples ofsuitable solvents or diluents are: ether and ethereal compounds, forexample diethyl ether, dipropyl ether, dioxane, dimethoxyethane andtetrahydrofurane; amides, such as N,N-dialkylated carboxamides;aliphatic, aromatic and halogenated hydrocarbons, especially benzene,toluene, xylenes, chloroform and chlorobenzene; nitriles, such asacetonitrile; dimethyl sulfoxide; and ketones, such as acetone andmethyl ethyl ketone.

The starting materials of formulae II to V are known or can be preparedby methods analogous to known ones.

The compounds of formula I are obtained in the form of a mixture ofdifferent optically active isomers if inhomogenous optically activestarting materials are used in the reaction. The different mixtures ofisomers can be separated into the individual isomers by known methods. Acompound of formula I is to be understood as comprising the individualisomers and the mixtures thereof.

The compounds of formula I are suitable for controlling a variety ofanimal and plant pests. The compounds of formula I can thus be used forcontrolling insects, for example of the orders: Lepidoptera, Coleoptera,Homopterea, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura,Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera andHymenoptera and mites and ticks of the order Acarina.

The compounds of formula I are particularly suitable for controllingplant-destructive insects, especially plant-destructive feeding insects,in ornamentals and crops of useful plants, in particular in cotton andrice crops (e.g. Spodoptera littoralis, Heliothis virescens, Nephotettixcincticeps, Nilaparvata lugens, Chilo suppressalis and Laodelphaxstriatellus) and in vegetable and fruit crops (e.g. Leptinotarsadecemlineata, Myzus persicae, Laspeyresia pomonella and Adoxophyesreticulana), and for controlling soil insects (e.g. Aulacophorafemoralis, Chortophila brassicae, Diabrotica balteata, Pachnoda savignyiand Scotia ypsilon).

The compounds of formula I are also very effective against flies, e.g.Musca domestica and mosquito larvae, and against ectoparasitic mites andticks, e.g. of the families Ixodidae, Argasidae and Dermanyssidae. Inaddition, the compounds of formula I have broad ovicidal andovolarvicidal activity.

The compounds of formula I also have excellent activity against insectsthat feed on keratin such as Lepidoptera larvae, e.g. Tineola spec. andTinea spec., and also Coleoptera larvae, e.g. Anthrenus spec. andAttagenus spec. The compounds of formula I are most suitable forprotecting keratinous material against feeding damage by insects,especially for providing such material with a washfast and lightfastprotective finish against insects, in particular moths and beetles. Thekeratinous material to be proctected can be both in the raw and in theprocessed state, for example raw or processed sheep's wool or productsmade of other animal hairs, hides, furs and feathers.

A particularly important feature is the effectiveness of the compoundsof formula I against the larvae of the webbing clothes moth (Tineolabisselliela) and the common clothes moth (Tinea pelionella) as well asagainst the larvae of fur beetles beetles (Attagenus spec. and Anthrenusspec. respectively). The compounds of formula I are thus preferred onthe one hand for protecting woollen textiles, for example blankets, woolcarpets, woollen underwear, woollen clothing, knits and wool-containingtextiles such as blends, one component of which is wool, for exampleblends of wool and other natural fibres, preferably cotton, and, on theother hand, for protecting furs and hides from attack by theabove-mentioned pests.

The acaricidal and/or insecticidal action can be substantially broadenedand adapted to prevailing circumstances by addition of otherinsecticides and/or acaricides. Examples of suitable addditives include:organophosphorus compounds, nitrophenols and derivatives thereof,formamidines, ureas, other pyrethroids, carbamates, and chlorinatedhydrocarbons.

Compounds of formula I are also combined with particular advantage withsubstances which exert a synergistic or potentiating effect onpyrethroids. Examples of such compounds include: piperonyl butoxide,propynyl ether, propynyl oximes, propynyl carbamates and propynylphosphates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamexor Sesoxane), S,S,S,-tributylphosphorotrithioate,1,2-methylenedioxy-4-(2-(octylsulfinyl)propyl)benzene.

The compounds of the formula I are used in unmodified form, orpreferably together with the adjuvants conventionally employed in theart of formulation, and are therefore formulated in known manner toemulsifiable concentrates, directly sprayable or dilutable solutions,dilute emulsions, wettable powders, soluble powders, dusts, granulates,and also encapsulations in e.g. polymer substances. As with the natureof the compositions, the methods of application such as spraying,atomising, dusting, scattering or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions or preparations containing thecompound (active ingredient) of formula I and, where appropriate, asolid or liquid adjuvant, are prepared in known manner, e.g. byhomogeneously mixing and/or grinding the active ingredients withextenders, e.g. solvents, solid carriers, and in some casessurface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycolmonomethyl or monoethyl ether, ketones such as cyclohexanone, stronglypolar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide ordimethyl formamide, as well as vegetable oils or epoxidised vegetableoils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. In addition, a great number of pregranulated materialsof inorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are nonionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained, e.g. from coconutoil or tallow oil. Further suitable surfactants are also the fatty acidmethyltaurin salts.

More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metalsalts, alkaline earth metal salts or unsubstituted or substitutedammonium salts and contain a C₈ -C₂₂ alkyl radical which also includesthe alkyl moiety of acyl radicals, e.g. the sodium or calcium salt oflignosulfonic acid, of dodecylsulfate, or of a mixture of fatty alcoholsulfates obtained from natural fatty acids. These compounds alsocomprise the salts of sulfuric acid esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and one fatty acid radicalcontaining 8 to 22 carbon atoms. Examples of alkylarylsulfonates are thesodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid,dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonicacid/formaldehyde condensation product. Also suitable are correspondingphosphates, e.g. salts of the phosphoric acid ester of an adduct ofp-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, or saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycolcontaining 1 to 10 carbon atoms in the alkyl chain, which adductscontain 20 to 250 ethylene glycol ether groups and 10 to 100 propyleneglycol ether groups. These compounds usually contain 1 to 5 ethyleneglycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylenesorbitan and polyoxyethylene sorbitan trioleate are also suitablenon-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals. The salts are preferably in the form ofhalides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammoniumchloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation aredescribed e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MCPublishing Corp., Ringwood, N.J., 1979, and Dr. Helmut Stache: "TensidTaschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981.

The pesticidal compositions usually contain 0.1 to 99%, preferably 0.1to 95%, of a compound of formula I, 1 to 99.9% of a solid or liquidadjuvant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant.

Whereas commercial products are preferably formulated as concentrates,the end user will normally employ dilute formulations.

The compositions may also contain further ingredients, such asstabilisers, antifoams, viscosity regulators, binders, tackifiers, aswell as fertilisers or other active ingredients for obtaining specialeffects.

Formulation Examples for liquid active ingredients of formula I(throughout, percentages are by weight)

    ______________________________________                                        1. Emulsifiable concentrates                                                                     (a)       (b)    (c)                                       ______________________________________                                        compound of formula I                                                                            25%       40%    50%                                       calcium dodecylbenzenesulfonate                                                                   5%        8%     6%                                       castor oil polyethylene glycol                                                                    5%       --     --                                        ether (36 moles of ethylene oxide)                                            tributylphenol polyethylene glycol                                                               --        12%     4%                                       ether (30 moles of ethylene oxide)                                            cyclohexanone      --        15%    20%                                       xylene mixture     65%       25%    20%                                       ______________________________________                                    

Emulsion of any required concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        2. Solutions       (a)    (b)    (c)   (d)                                    ______________________________________                                        compound of formula I                                                                            80%    10%    5%    95%                                    ethylene glycol monomethyl ether                                                                 20%    --     --    --                                     polyethylene glycol (mol. wt. 400)                                                               --     70%    --    --                                     N--methyl-2-pyrrolidone                                                                          --     20%    --    --                                     expoxidised coconut oil                                                                          --     --     1%     5%                                    ligroin (boiling range 160-190°)                                                          --     --     94%   --                                     ______________________________________                                    

These solutions are suitable for application in the form of micro-drops.

    ______________________________________                                        3. Granulates       (a)     (b)                                               ______________________________________                                        compound of formula I                                                                             5%      10%                                               kaolin              94%     --                                                highly dispersed silicic acid                                                                     1%      --                                                attapulgite         --      90%                                               ______________________________________                                    

The active ingredient is dissolved in methylene chloride, the solutionis sprayed onto the carrier, and the solvent is subsequently evaporatedoff in vacuo.

    ______________________________________                                        4. Dusts            (a)     (b)                                               ______________________________________                                        compound of formula I                                                                             2%      5%                                                highly dispersed silicic acid                                                                     1%      5%                                                talcum              97%     --                                                kaolin              --      90%                                               ______________________________________                                    

Ready for use dusts are obtained by intimately mixing the carriers withthe active ingredient.

Formulation Examples for solid active ingredients of formula I(throughout, percentages are by weight)

    ______________________________________                                        5. Wettable powders  (a)     (b)     (c)                                      ______________________________________                                        compound of formula I                                                                              25%     50%     75%                                      sodium lignosulfonate                                                                              5%       5%     --                                       sodium laurylsulfate 3%      --       5%                                      sodium diisobutylnaphthalenesulfonate                                                              --       6%     10%                                      octylphenol polyethylene glycol ether                                                              --       2%     --                                       (7-8 moles of ethylene oxide)                                                 highly dispersed silicic acid                                                                      5%      10%     10%                                      kaolin               62%     27%     --                                       ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        6. Emulsifiable concentrate                                                   ______________________________________                                        compound of formula I   10%                                                   octylphenol polyethylene glycol ether                                                                  3%                                                   (4-5 moles of ethylene oxide)                                                 calcium dodecylbenzenesulfonate                                                                        3%                                                   castor oil polyglycol ether                                                                            4%                                                   (36 moles of ethylene oxide)                                                  cyclohexanone           30%                                                   xylene mixture          50%                                                   ______________________________________                                    

Emulsions of any required concentration can be obtained from thisconcentrate by dulution with water.

    ______________________________________                                        7. Dusts             (a)    (b)                                               ______________________________________                                        compound of formula I                                                                               5%     8%                                               talcum               95%    --                                                kaolin               --     92%                                               ______________________________________                                    

Ready for use dusts are obtained by mixing the active ingredient withthe carriers, and grinding the mixture in a suitable mill.

    ______________________________________                                        8. Extruder granulate                                                         ______________________________________                                        compound of formula I                                                                             10%                                                       sodium lignosulfonate                                                                              2%                                                       carboxymethylcellulose                                                                             1%                                                       kaolin              87%                                                       ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        9. Coated granulate                                                           ______________________________________                                        compound of formula I  3%                                                     polyethylene glycol (mol. wt. 200)                                                                   3%                                                     kaolin                 94%                                                    ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        10. Suspension concentrate                                                    ______________________________________                                        compound of formula I   40%                                                   ethylene glycol         10%                                                   nonylphenol polyethylene glycol ether                                                                  6%                                                   (15 moles of ethylene oxide)                                                  sodium lignosulfonate   10%                                                   carboxymethylcellulose   1%                                                   37% aqueous formaldehyde solution                                                                     0.2%                                                  silicone oil in the form of a 75%                                                                     0.8%                                                  aqueous emulsion                                                              water                   32%                                                   ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water

EXAMPLE 1 Preparation of the compound of the formula ##STR4##

4.3 g of pyridine and 8.9 g of the compound of the formula ##STR5## in35 ml of toluene are added dropwise in succession at 0° C. to 6.7 g ofthe compound of the formula ##STR6## in 30 ml of toluene. The reactionmixture is stirred for 30 hours at 25° C. and then poured into 2Nhydrochloric acid and extracted with ether. The ethereal phase is washedwith a saturated solution of sodium bicarbonate and a saturated solutionof sodium chloride, dried over magnesium sulfate and concentrated. Theproduct is chromatographed through silica gel eluted with toluene/ethylacetate (95:5), affording the title compound (1) as a mixture ofdiastereoisomers with a melting point of 63°-64° C.

The following compounds can also be prepared in analogous manner:

    ______________________________________                                         ##STR7##                                                                     Comp. X.sub.1                                                                              R.sub.2 '  Physical data                                         ______________________________________                                         2    CH.sub.3                                                                             Cl         m.p.: 100-101° C.                               3    Cl     Cl         n.sub.D.sup.20°  = 1.5575                       4    CH.sub.3                                                                             Br         m.p.: 87˜88° C.                           5    Cl     Br         n.sub.D.sup.20°  = 1.5686                       6    CH.sub.3                                                                             J          n.sub.D.sup.21°  = 1.5609                       7    Cl     J          n.sub.D.sup.20°  = 1.5872                       8    CH.sub.3                                                                             F          m.p.: 96° C.                                    9    Cl     F          m.p.: 73° C.                                   10    CH.sub.3                                                                             CH.sub.3   m.p.: 94-96° C.                                11    CH.sub.3                                                                             OCH.sub.3  m.p.: 73-75° C.                                12    Cl     SCH.sub.3  n.sub.D.sup.27°  = 1.5749                      13    CH.sub.3                                                                             SCH.sub.3  m.p.: 52-54° C.                                14    Cl     OCH.sub.3  m.p.: 68-74° C.                                15    CH.sub.3                                                                             CHCH.sub.2 m.p.: 50-52° C.                                16    CH.sub.3                                                                             CCH        m.p.: 73-74° C.                                17    CH.sub.3                                                                             H          [α].sub.D = -41°(C = 0.33;                                       CHCl.sub.3)                                           18    CH.sub.3                                                                             H          [α].sub.D = +34.5°(C = 0.28;                                     CHCl.sub.3)                                           ______________________________________                                    

EXAMPLE 2 Insecticidal stomach poison action: Nilaparvata lugens

Rice plants are sprayed with a solution containing 50 or 100 ppm of testcompound.

After the spray coating has dried, the plants are populated with nymphsof Nilaparvata lugens in the N₃ stage. Two plants are used per testcompound and per test species. Evaluation of the mortality rate is made6 days later. The test is carried out at 22° C. and 60% relativehumidity. In this test, the compounds of Example 1 are 100% effectiveagainst nymphs of Nilaparvata lugens at a concentration of 50 ppm.

EXAMPLE 3 Action against Diabrotica balteata

750 ml of sandy soil are mixed with 150 ml of a solution containing 3,0.75, 0.2 or 0.05 ppm of test compound. Maize seedlings are put intoplastic pots filled with the treated soil (4 seedlings per pot, each pothaving a diameter of 10 cm). Immediately afterwards, the pots areinfested with 10 Diabrotica balteata larvae in the L₃ stage. Evaluationis made 10 days after infestation with the larvae.

In this test, the compounds of Example 1 are 100% effective againstDiabrotica blateata larvae in the L₃ stage at a concentration of 3 ppm.

EXAMPLE 4 Action against ticks (A) Amblyomma hebraeum

50 nymphs are counted into a test tube and immersed for 1 to 2 minutesin 2 ml of an aqueous emulsion prepared from a dilution seriescontaining 10, 1 or 0.1 ppm of test compound. The test tube is thensealed with a standard cotton wool plug and placed on its head to enablethe cotton wool to absorb the emulsion. Evaluation is made 1 week later.Each test is repeated twice.

(B) Boophilus microplus (larvae)

Tests are carried out with 20 OP-sensitive and 20 OP-resistant larvaeusing a dilution series similar to that used in Test A. (The resistancerefers to the tolerance towards diazinone). Compounds of Example 1 are100% effective against nymphs and larvae of the ticks Ambylomma hebraeumand Boophilus microplus at a concentration of 0.1 ppm.

EXAMPLE 5 Insecticidal stomach poison action: Spodoptera littoralis

Cotton plants are sprayed with a solution containing 100, 200 or 400 ppmof test compound. After the spray coating has dried, the plants arepopulated with Spodoptera littoralis larvae in the L₁ stage. Two plantsare used per test compound and per test species. Evaluation of themortality rate is made after 2, 4, 24 and 48 hours. The test is carriedout at 28° C. and 60% relative humidity. In this test, compounds ofExample 1 are 100% effective against Spodopterea littoralis larvae at aconcentration of 400 ppm.

EXAMPLE 6 Action against the webbing clothes moth, the fur beetle andthe carpet beetle (a) Exhaust method

A 0.4% stock solution of each of the compounds of Example 1 in methylcellosolve is prepared. Then an aqueous treatment bath containing, in120 ml of distilled water, 0.12 ml of Sandozin KB®, 0.6 ml of formicacid 1:10 and 0.75 ml of the respective 0.4% stock solution is preparedat room temperature. Then 3 g of wool flannel are wetted with hot waterand put into the bath at room temperature. While constantly circulatingthe wool sample, the bath temperature is raised to 60° C. in the courseof 20 minutes and treatment is carried out for 30 minutes at 60° C. Thebath is then cooled, the wool sample rinsed twice for 3 minutes withdistilled water, squeezed out by hand and dried in the air. The activeingredient concentration is 1000 ppm, based on the weight of the wool.

The dried sample is subjected to the moth-proofing test (protectionagainst feeding damage caused by the webbing clothes moth Tineolabiselliella Hum) and to the resistance test against larvae of the furbeetle (Attagenus piceus) and carpet beetle (Anthrenus voraxWaterhouse).

Pieces of the same size are cut out of the treated wool samples andsubjected for 14 days at constant temperature (28° C.) and constantrelative humidity (65%) to attack (feeding) by 15 larvae of each of thepests. Evaluation is made on the one hand according to the relative lossin weight of the test sample and, on the other, according to the numberof still living organisms.

The tested compound of Example 1 are 100% effective against all threepests.

(b) Pad method

A 0.4% stock solution in methyl cellosolve of each of the compounds ofExample 1 is prepared. Each stock solution (12.5 ml) is diluted to 50 ml(solution 1) with methyl cellosolve which contains 0.65 g/l of SandozinKB®. Solution 1 (25 ml) is diluted to 50 ml (solution 2) with methylcellosolve which contains 0.5 g/l of Sandozin KB®. Solution 2 (25 ml) isthen diluted in turn to 50 ml (solution 3) with methyl cellosolve whichcontains 0.5 g/l of Sandozin KB®.

3 ml of each of solutions 1, 2 and 3 are poured into crystallisationdishes and a disc of wool flannel is wetted for 3 seconds therein. Themoist discs are then padded between aluminium sheets to a pick-up of 50%of each solution. The active ingredient concentrations are,respectively, 500 ppm, 250 ppm and 125 ppm for the discs treated withsolutions 1, 2 and 3. The moist discs are then dried in the air andsubjected to the same biological tests as described in Example 6a.

The tested compounds of Example 1 are 100% effective against all threepests, even at the lowest concentration of 125 ppm.

What is claimed is:
 1. An α-methyl-(6-phenoxy)-2-picolylcyclopropanecarboxylate of the formula ##STR8## wherein R₁ is halogen,R₁is hydrogen or halogen, and R₂ is hydrogen, halogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, C₁-C₄ haloalkylthio, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, nitro or cyano.
 2. Acompound according to claim 1, whereinX₁ is methyl or chlorine, and R₂is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C4alkylthio,vinyl or ethynyl.
 3. A compound according to claim 2, whereinR₁ ishydrogen, and R₂ is hydrogen or halogen.
 4. The compound according toclaim 3 of the formula ##STR9##
 5. The compound according to claim 3 ofthe formula ##STR10##
 6. The compound according to claim 3 of theformula ##STR11##
 7. A pesticidal composition which comprises, as activeingredient, 0.1 to 99% of a compound according to claim 1, incombination with adjuvants conventionally employed in the art offormulation.
 8. A method of controlling a variety of pests of animalsand plants and soil pests, which comprises contacting said pests ortheir habitat with a pesticidally effective amount of a compound ofclaim 1.